Treatment of phosphate rock to recover phosphorus, fluorine, calcium, and uranium



c. A. HOLLINGSWORTH Dec. l1, 1956 TREATMENT OF' PHOSPHATE ROCK TO RECOVER PHOSPHORUS FLUORINE, CALCIUM, AND URANIUM Filed Aug. 8, 1952 W WAYQBKW y INVENTOR Z//v 70A/ A. /aLL/Nas www# ATTORNEYS TREATMENT OF PHOSPHAIIEROCK T RECOVER PHOSPHRUS, FLUORINE, CAlLCIUM, AND URANIUNI Clinton A. Hollingsworth, Lakeland',v Fla., assig'nor to- Smith-Douglass Company, Incorporated, Norfolk, Va., a corporation of Virginia Application August 8, 1952, Serial No. 303,270

Claims. (Cl. 23u-14.5)

carbonate (CaCOa), silica (SiOz), aluminum and iron` oxides (A1203 and Fe203), organic matter and minor other impurities. Some natural phosphate rocks contain aluminum oxide in substantial amount, probably combined with phosphorus in proportions to form aluminum' phos-l phate (AlzOa'PzO). v especially those containing substantalamounts of'aluminum phosphate, contain very small amounts of uranium.

The present invention contemplates the" recovery, in

marketable form, ofthe phosphorus, iiuorine,- calcium, uranium and aluminum (when present 1n substantial amount) contents of' phosphate rocks and' similar natural' phosphatic materials. To this end, the inventioninvolves heat-treating the phosphatic material in the presence" of a suitable reducing agent, such as a carbonaceous material, in an atmosphere containing ychlorine preferably in the form of dry hydrogen chloride (hydrochloric acid gas-HC1). The heat-treatment is carriedout a't'la temperature between 2000 and 2400'F., or'high'er, 'in

the chlorine-containing atmosphere until the uor'apati'te.

or other phosphate constituent lof the phosphatic nia-fterial has been reduced and phosphorusand tluorne havey been vol'atilized, leaving the calcium, uranium and aluminum in the residue. Fluorine volatilizes a's hydrogen uoride (hydrotiuoric acid-HP), and phosphorus'init'illy volatilizes mainly as elemental phosphorus, but under varying operatingconditions may be present in the gaseous l reaction product of the heat-'treatment as phosphorus 55 Iron volatilizes as ferrous or ferrie chloride, or

Calcium combines with chlorine to form calcium chloride (CaClz) which at'the trichlo'ride (PG13)v and/or Vphosphorus pentachloride (PCls). both (FeClz and/o1 FeCls).

temperature of heat-treatment remains in the residue in a molten state. Whatever uranium is presentin the phos-v phatic materialalso remains in the residue 'iu-the ,form

ofa water-soluble chloride (probably. a uranylchloride such as UOzClz) mainly associated with the molten call-V cium chloride. The residue also contains whatever .silica was present in the phosphatic material as well as any aluminum (principally in the form of aluminum oxide or alumina), and since the silica and alumina are solid and not lfused .at the temperature. of 'heat-treatment they may Most phosphate rocks, .and more 2,773,736 Patented Dec. 11, 1956 ice? be readily separated' from the molten calcium chloride and uranium content associated therewith.

In carrying out the process of the invention, the phosphate rock (or other natural phosphatic material) is usually inely divided. The preferred reducing agent is a carbonaceous material such as coal or coke, also nely' dividedand intimately mixed with the finely divided phosphate'rock. The mixture is preferably made into nodules or briquettes to facilitate handling, although the finely dividedY mixture may be directly heat-treated in suitable apparatus, as for example in a uo-solids operation. Although itfius generalily preferable to finely grind the phosphate rock` and coal in order to secure intimate contact ofV the chlorine-containing gas therewith, an intimate mixtur'eo'fv rock and-coal particles about 1/4 inch in size (e. g; Florida concentrates mostly minus 20 mesh standard Tyler screen) gives satisfactory results, and in a large scalel operation where the depth of the charge is relatively depevencoarser materials may be used.

The mixture of phosphatic and carbonaceous materials' should'contain at least 10% byv weight of carbon. When the amount of carbon in the mixture is below 10%, volatilaz'ation of phosphorus is incomplete, and for this reasonitis: advantageous and preferable to include from l5to 30%v by weight of carbon in the mixture of phosphatic andcarbonaceous materials. Theoretically, Vthe amount of carbon entering' into and consumed in the heatltreat'ment reactions should depend, to some extent at least, on the grade (i. e. P205 content) of the phosphatic material. However, in practicing the invention,

the aforementioned percentages of carbon exceed theamount theoretically requiredy for the treatment of phos-l phat'ic materials having a P205 content of from 2,5 to 40%, and 'such percentages of carbon are usually applicable to any phosphatic material within those grade lh. treating phosphatic materials of lower and higher grades, the percent of carbon mixed with the material may be correspondingly adjusted.

'The intimately mixed phosphatic and carbonaceouslmaterials are' heat-treated at a temperature between 2000 and 2400?' F., or higher, in an atmosphere containing chlorine. While temperatures up to 2400 `F. are adequate for' the purposes of the invention, higher temperatures 'are not harmful since the residue, for the -most part, may

be'fused or melted, if desired. The heat-treatment is continued 'untilsubs'tntially ,complete volatilizaton of uorino and phosphorus has been accomplished, v,which ,at a heat-treatment vtemperature of Z-2200* F. requiresa' detentionl period of from 10 to 30 minutes, and usually about 20 minutes. `Dry hydrochloric acid gas Vis the pre1-4 ferredl chlorine-containing atmosphere, although chlorine itself, ammonium chloride and equivalent gaseous agents containing chlorineor hydrogen chloride in available form may beused fto provide thene'cessary chlorine-containing atmosphere. When usingchlorine gas, it-is advisable'that some hydrogen :chloride or ammonium chloride .be used in conjunction: therewith. The Aamount Iof chlorine theoret'- icallyf. required to eiect ,the-contemplated chemical reactions idepends mainly iupon the lime (CaO) content of the? phosphatic material, since all `of the calcium of the-phosphaticmaterial is 'to be converted-"to calcium chloride However, suchtheoretical amount `of chlorine is inadequate for .the purposes of the invention, and in practicing the invention with charge `mixtures made up ofthe common phosphate rocks (having a P205 content vof v25-4 0%) and 10to-30%- by weight of coal, anamountjofchlorine I atleastequivalent to from 50 to 150 partsbywe'ight-for each .100parts .by weight ofthe charge mixture should-be` present in the chlorine-containing atmosphere. In practice an excess of chlorine is desirable to insure intimate and constant contact of the charge with chlorine during the entire period of heat-treatment and until uorine and phosphorus have been volatilized to the desired extent. Any excess of chlorine may be recovered from the gaseous product of the heat-treatment and recycled.

Heat-treatment is carried out in any suitable type of externally-heated retort or muflle equipped for the introduction of the chlorine-containing gas and the withdrawal of the gaseous reaction product. The retort or mule, as well as the other parts of the equipment coming in contact with chlorine-containing gases, are preferably made of, or lined with, graphite. Most of the uorine is evolved before substantial volatilization of phosphorus occurs, and in a batch operation this permits a rough selective condensation and separation of the evolved compounds of uorine and phosphorus from the gaseous reaction product. The over-all reactions of the heat-treatment'are exothermic, and the amount of external heating should be properly correlated to the amount of internal exothermic heating to avoid unnecessary or undue overheating of the charge.

Any suitable type of apparatus may be used in carrying out the heat-treatment such as a vertical shaft furnace, a travelling hearth furnace of either the tunnel or revolving type, a horizontal mule furnace etc. Preferably, heat-treatment is carried out as a continuous operation, although it may be conducted as a batch operation if desired. At the temperature of heat-treatment, the conventional refractory materials are attacked by the chlorinecontaining atmosphere and the hot gaseous reaction products, and hence all parts of the heating apparatus and its appurtenances coming in contact with such atmosphere' and products should be of graphite, carbon or equivalent refractory material. It is important that the heating apparatus permit intimate and continuous contact of the chlorine-containing atmosphere with the entire body of charge undergoing treatment until the contemplated volatilization of uorine and phosphorus has been accomplished. To this end, it is preferable to pass a stream o'f the chlorine-containing atmosphere over and through the entire body of the charge so that chlorine in the atmosphere contacting the charge is replaced as rapidly as it is consumed by reaction with the charge constituents, and in a continuous operation the relative movement of the chlorine-containing gas stream and the charge should be counter-currentwise.

The gaseous reaction product is withdrawn from the heat-treatment apparatus and conveyed to the condensing equipment. In a rst condenser, most of the evolved elemental phosphorous and phosphorus chlorides are recovered, and in a succeeding condenser most of the evolved hydrogen uoride is recovered. The exhaust gas of the fluorine 'condenser contains the excess of the hydrogen chloride or equivalent chlorine-containing gas employed in the heat-treatment as well as carbon monoxide (CO), hydrogen (H) and probably a minor amount of carbon dioxide (CO2) formed during the heat-treatment reactions. The hydrogen-chloride in the exhaust gas may be condensed, following the uorine condenser, and

recycled, and the carbon monoxide and hydrogen mayl be recovered or wasted depending upon local economics'. I The nature of. the reactions taking place duringheat-V treatment is complicated by the complex character of the phosphate rock, and further depends (to some extent at least) on the composition of the chlorine-containing atmosphere and the relative amounts of rock and carbonaceous material in the mixture undergoing treatment. While I am not prepared to state what these reactions are, itis my present belief that the initial reaction is a reduction of the iluorapatite in the rock with the volatilization of elemental phosphorus and perhaps elemental uorine. InV the presence of hydrogen chloride, the calcium liberated The theoretical charges and the theoretical amount of HCl required for the foregoing equations are as follows:

' -Percent 9Ca0-3Pa0s-CaFz 84.85 77.78 77.78 77.78 77.78

Percent 0 15.15 22.22 22.22 22.22 22. 22 Theoretical parts HC1 per 100 parts charge 61.45 56.33 81.6 107 56.5

., at the heat-treatment temperature.

charge mixture is formed into nodules, pellets, briquettesf j While there is positive evidence of the presence of carbon monoxide and hydrogen in the gaseous reaction product, it may well be that these substances are not actually present in the theoretical amounts indicated in the foregoing equations. Moreover, with a charge mixture containing 15 to 30% of carbon, there is always some carbon left in the residue from the heat-treatment, indicating an excess of carbon over and above the amount entering into and consumed inthe heat-treatment reactions.

Since economic practice of the invention requires intimate and continuous contact of the chlorinecontaining gas with the entire body of the charge mixture, a loose charge of finely divided materials should be rabbled or otherwise suitably stirred or agitated to insure that all parts of the charge are exposed to the action of chlorine Preferably, the

or other agglomerates (e. g. by agglomerating, briquetting, extruding or the like). The nodules etc. should be suciently porous to permit unimpeded penetration of chlorine into the interior thereof and free evolution of` the volatile products of the reaction from the interior' thereof to the ambient atmosphere, and to this end suitable porosity Vagents may be included in the charge mixture before nodulizing or the like. Advantageously, a`

-bituminous coking coal may be mixed with the phosphatic material, to supply the required carbon, and, after nodulizing or the like, the nodules or the like may be subjected to a low-temperature coking treatment in the course of which the volatile constituents of the coal are Idriven oi and porous coked nodules or the like are produced of adequate strength to withstand subsequentv handling.

The non-volatile residue of the heat-treatment corr-A sists of the molten calcium chloride and non-molten (i. e.

unfused) solid silica, alumina, residual carbon and minor amounts of other non-volatile substances present in the charge mixture of phosphatic and carbonaceous materials. original phosphatic material is associated with the molten calcium chloride in the form of a water soluble compound now believed to be a chloride or oxi-chloride. VAt i and well below the temperature of heat-treatment, thel molten and solid portions of the residue can be rea1.lily'` separated. In the preferred practice of the invention',t

Substantially al1 of the uranium present inthe' a. nedulized chareemirnre initiallycantaiin1-iis-l s. bituminous Cokina coal. asv the Source. et; eerbein die. residue willbe largely. in the forni. r honey-combed as gregates with molten, calcium chloride` in the interstices-A pararushrauslr. a star-Wheel. discharge. denies/1li into .i

Seated. anis, (.n9t-sh9wn9-.

Hydrogen suor-inc, or other suitable. chlorine-cnntain.`

ingress.. is. intrqdneedi through. a. Pipe 17 into the.; lowerfi thereof- From Such, a residue,v the molten portion is Part-.Ofthefretort 5.-, between. the perforated. disc 15 and easily separated from the unfused solid portion by aV dis .t: hc 1 rg e` fleyiluef1li.4 The gaseous'reaction; product; on Simple. draining. Operation, by decantation, byl ltration. theheaetreatnicnteis wither.awn.from4 the top partofthe. or the like. retort 5f through', an outlet pipe 18, and" rst passes. Chlorine for the practice of the invention is advane through. oneormorephosphorus condensers 19..and then: tageously produced electrolytically, andmay be reacted 10 through alluorine condenser 20. The exhaust. gas of` with electrolyticallyproduceclhydrogen to form hydro-r the norine eondense1';:iS Passed to a. Condenser 21 in chloric acid gas. The hydrochloric. acid. gas should. be which hydrogen ehlorideais condensed and thence dc. d ry when introducedY into the heat-treating apparatus, livered tota. Storage. receptacle 22 for hydrogenChlorideand. may, if desired, be. preheated to minimize any. Thegascous exhaust offthe condenser 21, whichA C0111 deleterious chilling eiect upon the charge mixture.` The tainS the-.carbonmonoxide and hydrogen formed duringV charge mixture itself. should be free of moisture, and to the hcattreatment,.may.be recovered in any Suitable Waythis end may be preheated prior to entering or introor- Inay beWased-l A PurnP 23 seri/@sfo draW the" duction into the chlorine-containing atmosphere. of Vheatgaseous reaetioIL Product fi'onlllle retort- 5' audioy foreel treatment. In this connection, mentionshould be made the gas; Stream tllfongllthe COndenSerS 19, and21.. of the fact that most raw phosphate rocksusually con- 20 Freshhydrogen- Cll'lol'ideis added as required to flle tain. considerable moisture, calcium and perhaps. other storagereceptacle. 22: A pump 24 withdraws hydrogeny oarbonates and organic matter, andv such rocks. are pref'- chloridethroughra-vaporizer 25 and delivers the result-4 erably calcined to. drive 0E the moisture and the. carbon inglr-ydrogen-chloride gasto the pipe 17. dioxide of the carbonates and to carbonize the organic The follow-ingexample illustrates a practice of the` i11- matter. Throughout this specication and vthe appended 25 ventionLin which the charge mixture; consisted of 70% claimsY it is to beunderstood that the phosphate rock orground phosphateV rock and bituminous coal. The. other phosphatic material entering into the charge mixcharge mixture was made into nodules about 1/2 inch in. tureis substantially free of moisture, and all amountsof size, and dried. The dried nodules were initially heatsuch materials herein recited are on a dryfbasi's. Similartreated at a temperature of 200G-2200" F. in an atly, the, carbonaceous material entering into the charge 30 mosphere of'nitrogen for about Sininutes to remove the'V mixture issubstantially free of moisture, and all amounts volatile constituents of the coal. Heattreatment ofthe thereof herein recited are on avdry basis. thus partially coked noduleswas then Carriedout at ay Silica in the charge mixture should be as low as practemperature of 2000-2000 F; for 90 minutes, in abatchticable, since excessive. silica has a deleteriousV inuence type operation, using hydrogen chloride in excessfor the on the chloridizing of both calcium andvuranium. Pref- 3a chlorine-containing atmosphere:

Analysis of rock and charge (calculated) P205 Insol. F9103 A1203. C80 F Ui Coall Rock percent.- 35.81 2.83 0.60 1.08 49.48 3.92 0.012 Charge dc 25.07 1.98 0.42 0.77 sa 64 2.74 0.0084 301.

erably, the silica content oi thechargemixture. does .not Approximately 85% of the phosphorus was volatilized.. exceed 6%,` by weight. By modern methods of concen- 45 VApproximately 90% of the iluorine was volatilized asy tration, phosphate plant products containing.. 3-3.5% hydrogen uoride. Substantially all of the calcium inthe silica (usually determined and designated as insoluble original rockwas present in the residue, mostly as molten-` matter in the phosphateindustry) are obtained, and such calcium chloride containing about 0.01% uranium.` The products may be advantageously used in the practiceof solid Portion of tlle residue consisted principally of 'ille-- theAinvention'. For the same reasons, carbonaceousma-.50 insoluble Constituents of tlle rook (mainly suina),y tenais of iew silica cement should vbe selected fer ad4` 'volatilized phosphorus and luorinc compounds and. mixture with the phosphatic material. residual carbon. About 75% by weight of the total;` lThe ,single .figure of the accompanying drawinggisa. residue Was Wafer-soluble, and reonsisled mainly of; Cal-.- sectional elevation of an apparatus, withA appurtenances Giuro Chloride The uranium Was in thiseWater-soluble;V diagrammatically shown, for-practicing the invention.V Part 0f the residue About 45% of the Wafer-insoluble.- The heHIEatiDg apparams illustrated in the d1-flawv part of the residue consisted of carbon. Substantially all. ngcomprises al cylindricaly vertical retort 5 made of of' h@ unvolatlhzed Phosphorus aud uol'me and somo-f graphite and surrounded by arlayer 6 of silicon carbide calcium was present in the Water-msoluble part of the.. The retort is mounted in a built-up furnace structurehav-- resldue ing K an inner heat ref1.actory portion 7 Such as .rhigh 60A The. gaseous reaction product leavingthe hot zone of. mperamrev brick, ,md an* Outer portions of 'insulating the. heat-treatmentapparatus has a'temperature'ofiabout. brick .or thellike. The furnace is. electrically heated' by 2000: F- For. efeelVe oondensatlon ofthe-volatilizeds resistanceelements 9. The charge mixture of phosphatic Phosphorus th? Phosphorus condense may have' an material and carbon, preferably.agglomeratedis.fed into Over'au. Operatmg tempelfaiure range of foulaboutfS". themprof the retort fmm a feed hopper lohrough a to about 536 F. The initial gaseous reaction product star-wheel feeding'devicell. Solid residues areremoved Should therefore be Subsfautlally Cooled before entering?.v from near the bottom of the retort Sinto a discharge.y the Phosphorus condenser 5111.65: the Volumef :the chute 12 by a reciprocating solids-discharge device 13 gaseous Produ.ct is not large, iSeooliug-Presens no SPeeiul' having a manipulating rod 14 which may be manually or Problem, and Cooling may be effected With ail OP Wafer automatically operated` applied to the exhaust flue 18, at anyy point between the A perforated graphite disc 15 is mounted within the retort 5 and the first phosphorus condenser. Suchcoolinggl lower part of therestort 5, immediately below. the solidsmay be advantageously effected inglalge. partfbyvlltilizing.; discharge ,device .13, to permit molten calcium chloride the heat yofthe gaseous productsto preheatzthe.ni'rdulizecly` and, Vassoci ated uraniumv chloride to `drain from.v the charge mixturein, the. unheated upper-.-partofiheretortf, residual charge, and thenceV discharged v from the ap- 75.l before thecharge enters the heated hotzone of theretorn In practice, the temperature of the gaseous reaction product as it leaves the retort 5,Y through the outletpipe 18, may thus be maintained at 60G-800 F. While it is believed that thephosphorus is present in the initial hot gaseous product mainly in the form of elemental phos phorus, some, or even all, of such elemental phosphorus may, in the presence of chlorine, be converted t-o'phosphorus chlorides. Elemental phosphorus condenses at about-536 F., phosphorus pentachloride condenses at about 320 F., and phosphorus trichloride condenses at about 167 F. By using more than one condenser, the elemental phosphorus can be -condensed separately from the phosphorus chlorides. For example, elemental phosphorus may be recovered in a first condenser operating at S-536" F., phosphorusk pentachloride may be recovered in a second condenser operating at 167-320 F., and phosphorus trichloride may be recovered in a third condenser operating at 68-167 F. Irrespective of its precise chemical composition, 85-98% of the phosphorus content of the phosphatic material of the charge is recovered in the liquid condensates withdrawn from the phosphorus condensers. The liquid condensates may be directly marketed as a raw source of phosphorus, or subjected to any appropriate subsequent treatment for producing other marketable phosphorus compounds.

Hydrogen uoride condenses at about 68 F., vand hence the operating temperature of the fluorine condenser is maintained not higher than, and preferably somewhat lower than, 68 F. Alternatively to condensing hydrogen luoride, the gas may be absorbed on sodium uoride. In either case, a concentrated tluorine product is obtained, which is directly marketable as a raw source of uorine. The exhaust gas of the uorine condenser 20 is passed to the condenser 21 where the excess hydrogen chloride gas is condensed, and the condensate conveyed to the receptacle 22. The exhaust gas of the condenser 21 is the residual gas from the heat-treatment and contains carbon materiaLis no believed best adapted for effecting the'A initial reduction of the uorapatite. But gaseous reduc-3 ing agents, such vas hydrogen, carbon monoxide and? hydrocarbons, may replace cold carbon in wholeorin In addition to'supplying the necessary chlorinefor lchloridizing the reduced calcium, the chlorine-contain? ing atmosphere so promotes the heat treatment reaction that reduction of the tluorapatite is effected at substantially lower temperatures than otherwise possible, where--y by the non-volatile residue of the heat treatment, other than the molten calcium chloride, remains unfused andr solid. Furthermore, by providing a large excess of,L chlorine (e. g. 150 parts or more per 100 parts of charge part.

mixture) elemental phosphorus is converted to a chlophosphorus. 'y

I claim:

1. The method of recovering values from a natural phosphatic material containing recoverable amounts of phosphorus, tluorine and calcium which comprises prepar-y monoxide, hydrogen, and possible some carbon dioxide.

Depending on local economic conditions, the carbon monoxide and hydrogen may be recovered from this residual gas for subsequent use, or the entire residual gas may be wasted.

The molten residue discharged from the retort 5 consists mainly -of calcium chloride containing around 0.01% of a water soluble uranium compound, probably an oxichloride (e. g. UOzClz). The uranium can be separated from the calcium chloride by methods of chemical precipitation or by ion exchange reaction, as for example by precipitation as an inorganic salt by ion exchange reaction with an organic resin, by extraction with an organic solvent, by reduction to a carbide as a furnace product, or by a combination of such methods. The molten residue is a marketable product on account of both its calcium chloride and uranium contents. Should the solid residue contain any substantial amount of phosphorus, there is a possibility that uranium will cornbine with and be tied up in such residual phosphorus, from which separation of the uranium is extremely diicult. Hence, in practice, volatilization of phosphorus is as nearly complete as practicable to minimize the amount of residual phosphorus in the solid residue. Where the phosphatic material of the inital charge mixture contains aluminum phosphate, the solid residue will contain laluminum oxide, in amount sutcient to warrant subsequent treatment of the residue as a raw source of alumina. 4

As hereinbefore stated, the initial reaction of the heattreatment is believed to be a chemical reduction of lluorapatite by the carbonaceous reducing agent admixed with the phosphatic material. The reduced phosphorus and uorine are volatilzed, and the reduced calcium combines with chlorine in .the chlorine-containing atmosphere to form calcium chloride which is molten at the temperature of heat-treatment. Form a practical standpoint, a solid reducing agent, such as carbon mixed with the phosphatic ing an intimate mixture consisting essentially of said ma- .i

terial and at least 10% by weight of a carbonaceous material, subjecting said mixture to heat-treatment for aperiod not exceeding minutes at a temperature within the range of 2000 to about 2400 F. in a chlorine-com` taining atmosphere selected from the class consisting of hydrogen chloride and ammonium chloride in which chlorine is present in excess of the amount theoretically required to convert all of the calcium in the phosphatic` material to calcium chloride, and subjecting the gaseous reaction product of the heat-treatment to selective con.

densation in which at least two condensates are obtained respectively consisting for the most part of the phosphorus and uorine contents of said gaseous reaction product, the non-volatile residue of said heat-treatment containing most of the calcium originally present in the phosphatic material in the form of molten calcium chloride.

2. The method of claim 1 in which the molten calcium chloride is separated from the unfused solid matter of the non-volatile residue of the heat-treatment.

3. The method of claim 2 in which the natural phosphatic material additionally contains a recoverable amount v of uranium, and recovering such uranium with the calcium chloride separated from the non-volatile residue of the heat-treatment.

4. The method of recovering values from a natural phosphatic material containing recoverable amounts of phosphorus, uorine and calcium which comprises preparing an intimate mixture consisting essentially of said material and from 15 to 30% by weight of a carbonaceous material, subjecting said mixture to heat-treatment for a period not exceeding 90 minutes at a temperature withiny ride from the unfused solid matter of the non-volatileY residue of said heat treatment.

5. The method of recovering values from a natural.`

phosphatic material containing recoverable amounts of phosphorus, fiuorine and calcium which comprises preparing an intimate mixture consisting essentially of said material and from 15 to 30% by weight of a carbonaceous material, subjecting said mixture to heat-treatment'for a period not exceeding 90 minutes at a temperature between about 2000fJ F. and about 2400 F. in an atmosphereof hydrogen chloride gas in which the amount by weight o f chlorinepresent is at least the equivalent of from 50 to .150

parts per parts'of said mixture, subjecting the gaseousreaction product of the heat-treatment to selective con- References Cited in the le of this patent densation in which at least two condensates are obtained UNITED STATES PATENTS respectively consisting for the most part of the phosphorus and fluorine contents of said gaseous reaction product, and 2'531046 Hollingsworth NOV' 21 1950 separating molten calcium chloride from `the unfused solid 5 matter of the non-volatile residue of said heat-treatment. FOREIGN PATENTS 7,636 Great Britain Feb. 16, 1895 

1. THE METHOD OF RECOVERING VALUES FROM A NATURAL PHOSPHATIC MATERIAL CONTAINING RECOVERABLE AMOUNTS OF PHOSPHORUS, FLUORINE AND CALCIUM WHICH COMPRISES PREPARING AN INTIMATE MIXTURE CONSISTING ESSENTIALLY OF SAID MATERIAL AND AT LEAST 10% BY WEIGHT OF A CARBONACEOUS MATERIAL, SUBJECTING SAID MIXTURE TO HEAT-TREATMENT FOR A PERIOD NOT EXCEEDING 90 MINUTES AT A TEMPERATURE WITHIN THE RANGE OF 2000 TO ABOUT 2400* F. IN A CHLORINE-CONTAINING ATMOSPHERE SELECTED FROM THE CLASS CONSISTING OF HYDROGEN CHLORIDE AND AMMONIUM CHLORIDE IN WHICH CHLORINE IS PRESENT IN EXCESS OF THE AMOUNT THEORETICALLY REQUIRED TO CONVERT ALL OF THE CALCIUM IN THE PHOSPHATIC MATERIAL TO CALCIUM CHLORIDE, AND SUBJECTING THE GASEOUS REACTION PRODUCT OF THE HEAT-TREATMENT TO SELECTIVE CONDENSATION IN WHICH AT LEAST TWO CONDENSATES ARE OBTAINED
 2. THE METHOD OF CLAIM 1 IN WHICH THE MOLTEN CALCIUM CHLORIDE IS SEPARATED FROM THE UNFUSED SOLID MATTER OF THE NON-VOLATILE RESIDUE OF THE HEAT-TREATMENT.
 3. THE METHOD OF CLAIM 2 IN WHICH THE NATURAL PHOSPHATIC MATERIAL ADDITIONALLY CONTAINS A RECOVERABLE AMOUNT OF URANIUM, AND RECOVERING SUCH URANIUM WITH THE CALCIUM CHLORIDE SEPARATED FROM THE NON-VOLATILE RESIDUE OF THE HEAT-TREATMENT. 